Certificate of correction



United iSQTHlURUr llll David '31, her, liin Henry W. Fons, l

This invention relates to new dyestuffs and to the coloring ofcellulosic and other textile materials therewith. in one specificaspect, it relates to new water-soluble dyestufis having attachedthereto at least one isothiuronium salt of a bromohydrin ether.

In recent years there has been considerable interest in the manufactureof Water-soluble dyestuffs containing triazine or pyrimidine ringstowhich there are attached reactive holog-en atoms. These classes ofdyestuffs are believed to react with the functional groups of cellulosicand other fibers and, as a result, give colorations which are extremelyresistant to wet treatments. The dyestuffs must contain at least oneionogenic solubilizing group, e.g., sulfonic acid or carboxylic acidgroups, to make them sufiiciently water-soluble to be applied from anaqueous bath. The requirement for at least one sulfonic acid orcarboxyiic acid group thus imposes a limitation on the type of coloredcompound that can be used to synthesize the dyestuffs.

We have found that unexpectedly superior water-soluble dyestuffs can bemade from water-insoluble dyestufls, free of ionogenic solubilizinggroups, by converting waterinsoluble dyestuffs containing a bromohydrinether group to isothiuroniurn salts. Our new dyestuffs, when applied tocellulose or other textiles by dyeing or printing in the presence of anacid-binding agent, give bright colorations which have good washfastness.

It is therefore an object of the present invention to provide a newclass of Water-insoluble dyestuffs having attached thereto at least oneisothiuronium salt of a bromohydrin ether group.

In accordance with the invention, we have discovered dyestuffs of theformula wherein Z is a water-insoluble colored moiety of the azo,anthraquinone, phthalocyanine or nitro series as recognized by theColour Index, 2nd Edition, 1956; it is a small, whole number having avalue from 1-4; R and R as individual substituents, are members selectedfrom the group consisting of hydrogen and lower alliyl and, takencollectively, they represent an alkylene bridge having from 2-3 carbonatoms, said bridge connecting the N atoms to which R and R are attached;and R and R are hydrogen or lower alkyl. The Z term, representing thedystuff moiety, is free of ionogenic solubilizing groups.

The new dyestuffs are made by the interaction of one mole of awater-insoluble hydroXyl-containing colorant of the azo, anthraquinone,phthalocyanine or nitro series with at least one mole of epibromohyclrinper hydroxyl group to form a water-insoluble bromohydrin ether dyestuff.This intermediate is converted to the water-soluble isothiuroniurn saltby reacting it with a thiourea.

In lieu of the epiohloroor epibrornohydrin used to prepare the2-hydroxy-3-bromopropoxy intermediates, the hydroXy-containing colorantscan be reacted with an allyl halide, e.g., allyl chloride or allylbromide, to form an rates Patent 0 h e-tented Nov. 3, 196% ice allylamine which, by reaction with hypobrornous acid, is converted to anintermediate useful in the invention.

The water-insoluble hydroxyl-containing colorants of the azo seriessuitable for making the dyestufiis of the invention are made bycoupling, with any suitable coupling component, phenol, substitutedphenois having an open 0- or p-position, o-cresol, p-cresol, substitutedcresols with an open oor p-position, xylenol, resorcinol, pyrogallol,amino phenols, l-naphthol and substituted l-naphthols, Z-naphthol andsubstituted Z-naphthols, 2 methyLB-quinolinol, 8-quinolinol,2,4-quinolinediol and N,ll-diall ylanilines in which at least one of thealkyl groups contains an hydroxyl function.

Specific useful hydroxyl-containing colorants include, but are notlimited to, aniliiie phenol; l-naphthylamine phenol; picrarnicacidphenol; picramic acid p-chlorophenol; picramicacidp-hydroxyacetanilide; anilineeo-cresol; picramic acidocresol;anilinecresol; p-arninoacetanilide p-cresol; o-toluidine p-cresol;p-phenetidineep-cresol; picramic :acid-ep-cresol; picramic acid-6-hydroXy-m-acetotoluidide; picramic acid 2,4-Xylenol; anlineresorcinol; 2-amino-4-nitrophenyl resorcinol; aniline pyrogallol;p-nitroanilinepyrogallol; N,N-dimethyl-p-phenylene-diaminepyrogal lol;p-zaminophenylpyrogallol; anilinel-naphthol; otoluitline- 1-naphtho1;p-phenetidine-e l-naphthol; picramic asid 5,6,7,8-tetrahydro-2-naphthol;aniline- 2- naphthol; o-nitrozn1iline- Z-naphthol; m-nitroaniline- 2-naphthol; p-nitroanilineeZ-naphthol; a copper complex derived fromp-nitroanilineeZ-naphthol; 2,4-dinitroaniline Z-naphthol;S-chloro-Z-nitroanlline 2-naphthol; 2- chloro-4-nitroaniline-Z-naphthol; 4-chloro-2-nitroaniline 2-naphthol; o-toluidine-aZ-naphthol; S-nitro-o-toluidine 2-naphthol; Z-nitro-p-toluidine-Z-naphthol; 2-nitro-4- trifiuoromethylanilinee Z-naphthol; 2,4-XylidineZ-naphthol; o-anisidine 2-naphthol; 5-chloro-o-anisidine 2- naphthol;cresidine-- Z-naphthol; 4-nitro-o-anisidine- 2- naphthol;5-nitro-o-anisidine Z-naphthol; l-naphthylan1ine- Z-naphthol;Z-naphthylaminee Z-naphthol; Z-amino-4,6-dichlorophenol Z-naphthol;Z-arnino-fi-nitrophenol- 2-naphthol; picramic acid-+2-naphthol;tolusafranine C15 0240 Z-naphthol; N,N-diethyltolusafranine- Z-naphthol;o-chloroanilinee 3-hydroxy-2-naphthanilide; rn-chloroaniline3-hydroxy-2-naphthanilide; 2,5-dichloroaniline3-hydroXy-2-naphtlranilide; S-nitro-o-toluidine3-hydroxy-2-naphthanilide; 3-amino-p-anisanilide-w3-hydroXy-2-naphthanilide; 34amino-p-t0lu-2,4-Xylidide-4-chloro-3-hydroxy-2-napthanilide; 5-nitro-o-toluidine-4'-chloro-3-hydroXy-2-naphthanilide; 2-nitro-p-toluidinc-3'hydroxy-3'-nitro-2-naphthanilide; 5-nitro-o-anisidine-aS-hydroxy-B-nitro-2-naphthanilide; 3-amino-p-anisanilide 3-hydroxy-3'-nitro-2-naphthanilide; 2,4,5 -trichloroani line3-hydroXy-Znaphtho-o-toluidide; 4-chloro-2-nitroanilinee3-hydroXy-2-naphtho-o-toluidide; 4-nitro-o-toluidine3-hydroxy-2-naphtho-o-toluidide; S-nitro-o-toluidine3-hydroxy-2-naphtho-o-to1uidide; 2 nitro-'p-toluidine3-hydroxy-2-naphtho-o-toluidide; 4-nitro-o-anisidine-3hydroxy-Z-naphtho-o-toluidide; Z-nitro-p anisidineH 3-hydroxy-Zmaphtho-o-toluidide; 4chloro-o-toluicline 4-chloro-3-hydroxy2-naphtho-o-to1uidide; 5chloro-o-toluidinee 5-chloro-3-hydroxy-2-naphtho-o-toluidide; 2,5 -dichloroaniline3-hydroxy-Z-naphtho-p-toluidide; m-amino-N-butylbenzarnide e3-hydroxy-2-naphtho-p-toluidide; 5 phenylsulfonyl 0 anisidine 3 hydroXy2 naph tho 2,3xylidide; S-benzylsulfonyl-o-anisidine 3 hydroxy-Z-naphthoQ,3-xylidide; 2,5-dichloroaniline+3-hydroxy-Z-naphth-o-phenetidide; 2,4-dichloroaniline-3-hydroXy-2-naphth-o-anisidide; 4-chlor0-2-nitroaniline-93-hydroxy-Z-naphth-o-anisidide; N ,N -diethyl-4-methoxymetanilamide e5-chloro-3-hydroXy-2,4'-dimeth0Xy-2-naphthanilide; 4-nitro-o-anisidine3-hydroXy-N-( 1-naphthly)- Z-naphthainide; 2-nitro-p-anisidine- 3hydroxy N (1- a naphthyl)-2-naphthamide; aniline- 2,4-quinolinediol;pchloroaniline 2,4-quinolinediol; o-nitroanilinee 2,4-quinolinediol;4-chloro-o-toluidine 2-hydroXy-2-5-dimeth- I oxy 3dibenzofurancarboxanilide; m-chloroaniline- 4-chloro-2-hydroXy-3-carbazolecarboxanilide; 2,4-dichloro' aniline-4-chloro-2-hydroXy-3-carbazolecarboxanilide; 2, 4-dichloroaniline4-chloro-2-hydroXy-3-carbazolecarb oxanilide; o-toluidine-e4-chloro-2-hydroXy-3-carbazolecarboxanilide; 3-amino-p-anisanilidide4-chloro-2-hy droxy-Z-carbazolecarboxanilide; O-IlltIOMfiHHB-MECEtOfiCE-tanilide; p-nitroaniline acetoacetanilide; 4chloro-2-nitroanilineacetoacetanilide; 2-nitro-p-toluidine aceto acetanilide;Z-nitro-p-anisidineacetoacetanilide; 2-amino-4-nitrophenolacetoacetanilide; 4-chloro-2-nitroanilineo-chloroacetoacetanilide; 2-nitro-p-toluidine 'o acetoacetotoluidide;2-nitro-p-anisidine-eoacetoacetotoluidide; 4-chloro-2-nitroaniline+2,4-acetoacetoxylidide; Z-nitno-ptoluidine2,4-acetoacetoxylidide; 2-nitro-p-anisidine oacetoacetanisidide;1-amino-3-bromoanthraquinone- 2,5-dirnethoxyacetoacetanilide-2,4,S-trichloroaniline 4-chlo- Io-2,5-dimethoxyacetoacetanilide and 4-chlor0-o-toluidine4-chloro-2,S-dimethoxyacetoacetanilide.

Other useful couplers which can be used, as indicated hereabove, to makeintermediates for the compounds of the invention include,1,5-dihydroxynaphthalene, 1,8-dihydroxynaphthalene,1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene and anthrols such aslanthrol and 2- anthrol.

Additional useful couplers mino)diethanol, 2 m-toluidinoethano1,2,2-(m-tolylimino) diethanol, 2- (N-methyl-m-toluidino) ethanol, 2-(N-methylanilino) ethanol, 2 (N-ethylan'nino)ethanol, 2,2-(m-chlorophenylimino diethanol, 2- (N-n-butyl-m-toluidino)ethanol,2-(N-n-butylanilino)ethanol, Z-N-nbutyl-6-methoXy-m-toluidino)ethanol,S-anilino-l 2-propanediol, 3-N-ethylanilino-1,2-propanediol,{3-(N-2-hydroxyethyl m toluidino)propionitrile,B-(N-Z-hydroxyethylanilino)propionitrile, andl-sec-butyl-l,2,3,4,-tetrahydro-7-methyl-3-quinolinol.

Disazo dyestuffs useful as intermediates in the invention includep-aminoacetaniiide (2 moles): m-phenylenediamine, then hydrolyze theacetamido groups, or p-nitroaniline (2 moles)jm-phenylenediamine, thenreduce the nitro groups with sodium sulfide; aniline (2 moles):zo-cresole; 2,4-Xyiidine (2 moles)3resorcinol; aniline (2 moles):fustic extract (Maclurin and Morin C175 240 and 75660); 2,4-dichloroaniline (2 moles): 4,4-bi-- acetotoluidide; S-chloro-o-toluidine (2moles)::; 4,4- bi-o-acetoacetotoluidide; 4-rnethoxy-m-phenylenediamineni-phenylenediamine (2 moles); 2,4-biphenyldiamine rip-isohexylphenol (2moles); benzidinezresorcinol (2 moles);3,3'-dichlorobenzidine3acetoacetanilide (2 moles); 3,3'dichlorobenzidinejo acetoacetotoluidide (2 moles);o-tolidineZacetoracetanilide (2 moles); o-tolidine:o-acetoacetotoluidide(2 moles); o-tolidine: resorcinol (2 moles);=o-dianisidine3acetoacetanilide (2 moles);o-dianisidine32,4-acetoacetoxylidide (2 moles); o-dianisidine3-hydroxy-2-naphthani1ide (2 moles); 4,4 cycloheXylidenedi-o-toluidine:zp-cyclohexylphenol (2 moles); 4,4'-benzylidenedi-2,S-xylidene p-cresol(2 moles); 4,4-(o-chlorobenzylidene)di-2,5-xyliinez; Z-naphthol- (2moles); 4,4'-benZylidenedi-o-anisidine3 Z-naphthol (2 moles);4,4-diaminodiphenylaminez;pisohexylphenol (2 moles); 4,4diaminothiocarhanilide jphenol (2 moles); p-phenylazoanilinephenol; 4-0-tolylazo-mtoluidine-a phenol; aniline- 1 naphthylamine phenol;p-phenylazoaniline o-cresol; p-phenylazoaniline Z-naphthol;4-o-tolylazo-o-toluidine Z-naphthol; otoluidine- 2,5 -xylidineZ-naphthol; xylylazoxylidine 2- naphthol.

Useful hydroxyl-containing anthraquinones include N- [2(Bahydroxyanthraquinonyl) ]-l -nitro-2'-anthraquinonetcarboxamide,4-anilino-5-nitrochrysazin, 4-aniline-8-nitroanthrarufin,l-hydroxy-4-(p-toluino) anthraquinone, 4- [m(l-hydroxyethylyanilino]-8-nitroanthrarufin, l-hyinclude:2,2-(phenylidroxyanthraquinone, Z-bnomoquinizarin,2,3-dihydroxyquinizarin, 2-chloroquinizarin, quinizarin,2-nitroquinizarin, 4,8-dinitro anthrarufin,1,4-bis(2-hydroxyethylamino)- 5,8-dihydroxyanthraquinone,l,2-dianilino-4-hydroxyanthraquinone, 4,8-diaminoanthrarufin,l-amino-4-hydroxyanthnaquinone, 1-amino-2-(Z-hydnoxyethylmercapto)-4-hydroxyanthraquinone, 1 amino-Z-bromo 4 hydroxyanthraquinone,l-amino-2-phenoxy-4-hydroxyanthraquinone,1-anilino-4-hydr0xyanthraquinone, chrysazin, anthrarufin,l-arnino-Z-methoxy-4-hydroxyanthnaquinone, 1-arnino-Z-ethoXy-4-hydroxyanthraquinone,l-amino-Z-benxyioxy-4-hydroxyanthraquinone, liamino-2-(2-hydroxyethoxy)-4-hydroxyanthraquinone, 1-amino-2-(Z-methoxyethoxy)-4-hydroxyanthraquinone,l-amino-Z-methylmercapto-4-hydroxyanthraquinone,1-arnino-2-ethylmercapto 4-hydroxyanthraquinone,l-arnino-Z-ethylmercapto-4-hydroxyanthraquinone, 1-amino-2-o-tolymercapto) -4-hydroxyanthraquinone,l-amino-2-(p-chlorobenzylmercapto)-4-hydroxya,nthraquinone,1-amino-2,3-diehloro-4-hydrexyanthraquinone,l,4,5,8-tetnahydroxyanthraquinom 4,8-diamino-2,S-dimethoxyanthrarufin,4,5-di amino-2,7- diphenoxychrysazin,l-methylamino-4-hydroxyanthraquinone,l-amino-2-methyl-4-hydroxyanthraquinone,1-benzamide-4-hydroxyanthraquinone, l-acetamido-4-hydroxyanthraquinone,l-benzamido-5-hydroxyanthraquinone,lpropionamido-S-hydroxyanthraquinone, 4,8-dianilinoanthrarufin,4,5-di-p-toluidinochrysazin, -1-hydroXy-4-cyclohexylaminoanthraquinone,l-(p-hydnoxyanilino)anthraquinone, 1-1ydroxy-4- (p-hydroxyanilino)anthraquinone, l-amino-4-(p-hydroxyanilino)anthraquinone, l-rnethylamino-4- (p-hydroxyanilino anthraquinone, 1- (p-chlorobenzamido) -4-(p-hydroxyanilino) anthraquinone.

Colorants of the phthalocyanine series useful in making the dyestuffsor" the invention are those free of ionogenic solubilizing groups whichcontain at least one hydroxyl group. The hydroxyl group may be attacheddirectly to the benz-rings of the phthalocyanine nucleus or it may beattached through a divalent bridging radical. The useful phthalocyaninesare made by conventional methods, e.g., by heating together a mixture ofthe appropriate phthalic acid derivative, urea, and cupric chloride inodichlorobenzene at about C. For example, the tetra(-p-hydroxyphenoxy)phthalocyanine is made by preparing thephthalocyanine by the foregoing method from the nitrophenoXy-phthalicacid, reducing the nitro group to an amino group and thereafterconverting the amino group to a hydroXyl group. Alternatively, mono-,di-, trior tetrahydroxy-substituted phthalocyanines can be made from thecorresponding mono-, di-, trior tetra(chlorosulfonated)pththalocyanineby reacting it with an aminophenol.

Useful colorants of the nitro series include picric acid,2,4-dinitrophenol and the hydroXy-substituted derivatives ofdiphenylarnines and phenyinaphthylamines, such as 2,4-dinitro-4'-hydroxydiphenylamine, 5-(2,4-dinitrophenyl)amino-Z-naphthol and the like. These derivatives are conveniently madeby condensing an arylamine containing a'hydrolyzable group, such asacylamido, With an aryl halide containing nitro groups in the 0- orp-positions, e.g., 2,4-dinitrochlorobenzene, then hydrolyzing theproduct to the free arylamine. The arylamine is then diazotized and thediazonium salt decomposed in hot acidic aqueous solution to provide thehydroxyl compound.

Thioureas from Which the isothiuronium salts of the invention can bemade include thiourea, ethylenethiourea, N,-N-dimethylthiourea,N,N,N-trimethylthiourea, and N, N,N, -tetramethylthiourea.

In preparing the dyestuffs of the invention the desiredhydroxyl-containing colorant of the azo, anthraquinone, phthalocyanineor nitro series is reacted with at least one mole of epibromohydrin perhydroxyl group, as shown hereunder, to formthe halohydrin ether.

Conveniently, the reaction is accomplished by reacting an excess ofepibromohydrin with the hydroxylated material at about 100 C. in thepresence of a catalytic amount of base, such as piperidine. Afterdistilling off excess epibromohydrin, the residue is dissolved in asuitable inert solvent, e.g., chlorofrom, shaken with aqueoushydrobromic acid to convert any glycidyl ether to the bromohythin, andthe product isolated by distilling off the solvent after separating fromthe aqueous layer and washing until neutral. Alternatively, there may beused an inorganic alkali, e.g., sodium hydroxide. The remainder of thepreparation is similar to the procedure just detailed.

During the preparation of the halohydrin ether, it is de sirable thatthe colorants containing free amino groups be used in the form of theiracylamido derivatives in order to protect the amino group from reactionwith the halohydrin and thus minimize undesirable side reactions.

Isothiuroniurn salts are formed from the bromohydrin ether according tothe following equation:

Z, R R R and R have the values given aforesaid. The reaction isconducted at a temperature between 60 and 125 C. either in aqueousslurry or in a solution using a suitable solvent, such as dioxane or alower alkanol. The product is recovered from the aqueous reactionmixture by drowning the mixture in a large excess of acetone or bysalting out the product with an inorganic salt, such as sodium chloride.If a solvent is used, the dyestuff precipitates from the reactionmixture and is recovered by filtration. The dyestuff thus obtained isoven dried and is thereafter ready for use.

The new dyestuffs of the invention are especially suited for thecoloration of cellulosic textile materials such as cotton, linen, andviscose rayon, although they also may be effectively applied to silk,wool, nylon and the like.

The dyestuffs are applied by treating the textile material in an aqueoussolution (which may be a thickened printing paste) of the dyestuff inthe presence of an acidbinding agent, for example, sodium hydroxide,sodium phosphate, or sodium carbonate. The acid-binding agent may beadded to the dye bath either prior to, simultaneously with, or after theaddition of the dyestuff.

The dyestufl? solution may contain commonly used dye bath adjuvants suchas sodium chloride, sodium sulfate, sodium alginate, urea orwater-soluble alkyl ethers of cellulose.

The printing paste may contain commonly used adjuvants, such as urea,and thickening agents, e.g., methyl cellulose, starch, locust bean gum,and sodium alginate.

Dyeing in the presence of the acid-binding agent is preferably carriedout at elevated temperatures, for example, at temperatures between 60 C.and the boiling point of the dyestutf solution in order to improve theexhaustion and fixation of the dyestufi.

The textile material printed with printing paste containing anacid-binding agent is preferably steamed or heated in order to fix thedyestulf on the textile material.

When the acid-binding agent is applied to the textile material before orafter the dyestuff, it is preferably applied by treating the fiber withan aqueous solution of the acid-bindins agent, i.e., a paddingtechnique. The aqueous solution of acid-binding agents may also containthe common dye bath adjuvants.

Both the solution of acid-binding agent and dyestuff may be applied atroom temperature or at elevated temperatures. The textile material canbe dried between the two treatments if desired. It is preferred to heator steam cellulosic material at an elevated temperature, for

example, at 100 C. or higher, for a short period of time afterapplication of the dyestuff and acid-binding agent to fix the dyestuffon the textile material.

The above techniques may be modified by substituting for theacid-binding agent a substance which on heating or steaming generates anacid-binding agent. Such substances include alkali metal bicarbonateswhich on steaming yield alkali metal carbonates.

The fastness to washing or subsequent wet processing of the colorationsproduced using our new dyestuffs is improved by a scouring treatment,e.g., applying a hot aqueous solution of soap and sodium carbonatefollowed by rinsing in hot water prior to drying.

The new dyestuffs may also be applied to silk, wool, regeneratedprotein, nylon and modified polyacrylonitrile textile materials by usingthe conventional dyeing methods for those textile materials, i.e.,dyeing from weakly acid dyebath solutions, for example, dyestuffsolutions containing acetic acid or ammonium sulfate at a te1nperatureabove C. When dyeting proteinaceous fibers in conjunction with an acidiccatalyst, it is preferable to use a temperature between 80 C. and C.

Our invention is further illustrated by the following examples:

Example 1 Z-rnethoxy-S-nitroaniline is diazotized and coupled into,B-naphthol. A mixture of 9.7 g. (0.030 mole) of the coupling productand 12.3 g. (0.090 mole) of epibromohydrin is stirred and held at 97-105C. for six hours in the presence of a trace of piperidine. Afterdistilling the excess epibromohydrin under vacuum, the residue isdissolved in chloroform and shaken with 48% hydrobromic acid. Thistreatment converts any epoxide which may have formed into the desiredbromohydrin. After washing neutral with water, the solvent is distilledunder vacuum and the residue is dried at 50 C. under vacuum.

The isothiuronium salt of the bromohydrin so formed is prepared asfollows: A mixture of 9.2 g. of the bromohydrin, 7.6 g. of thiourea and6 ml. of Water is stirred at 95 C. until a sample is soluble in water.The mixture is cooled, then added to 250 ml. of acetone. Theprecipitated product is triturated with acetone and washed well withfresh portions of that solvent, then dried at 50 C. under vacuum. Thereis obtained 6.7 g. (63% yield, based on the coupling product) ofyellow-orangecolored dye.

Example 11 A 1% solution of the dye of Example I is prepared in waterand used to pad 80 x 80 print cloth. After an intermediate dying, aportion of the padded cloth is padded a second time with a solution of 5g. of sodium hydroxide and 200 g. of sodium chloride per liter, thensteamed for 60 seconds. A second portion of the cloth padded with dye isalso padded with the sodium hydroxide-sodium chloride solution and heldfor three minutes in an oven at C. After rinsing, each of the dyedsamples exhibits very good wash fastness when tested with hot alkalinesoap solution.

Example III 4-chloro-o-toluidine is diazotized and coupled into 4'-chloro-3-hydroxy-2-naphthol-o-toluidide. By condensing this product withepibromohydrin according to the pro- 2 Example IV The procedure ofExample II is followed using a 1% solution of the dye of Example III.The fastness of the dyeing to soaping is once again much greater thanthat of the colorant from which the new dyestutI is prepared.

Example V The procedure of Example III is repeated using 1-(2- methoxy 4nitrophenylazo) 2 (3-bromo-2-hydroxypropoxy)-3-naphthianilide as astarting material. There is obtained in good yield a bluish-red dye.

Example VI The procedure of Example III is repeated using 3- brorno-1[4-N,N-bis(3-bron1o-2-hydroxypropoxyethyl)- anilinoazo1anthraquinone asa starting material. There is obtained in good yield a purple dye.

Example VII The procedure of Example III is repeated using 4,4- bis[2-(3-bromo-2-hydroxypropoxy) 1-naphthylazo]3,3'- dichlorobiphenyl as astarting material. There is obtained in good yield a reddish-violet dye.

Example VIII The procedure of Example III is repeated using 2-(3-bromo-3-hydroxypropoxy)-1-(2,5 dichlorophenylazo -3- naphtho-p-toluidideas a starting material. There is obtained in good yield a bluish-reddye.

Example IX The procedure of Example III is repeated using 8-(4-nitrophenylazo) (3-bromo 2 hydroxypropoxy)-1- naphthol as a startingmaterial. There is obtained in good yield a scarlet dye.

Example X 4,8-dianilinoanthrarufin is condensed with epibromohydrinaccording to the procedure in Example I to form the correspondingbis(bromohydrin ether).

A mixture of 20.9 g. (0.030 mole) of the bis-bromohydrin, 15.8 g. (0.12mole) of N,N,N',N-tetramethy1- thiourea, and 12 ml. of Water is stirredand heated at 95 C. until a sample is water-soluble. After adding thereaction mixture to an excess of acetone, triturating the precipitatedproduct with fresh portions of acetone, filtering oil the solid, anddrying it at 50 C. under vacuum, there is obtained 24.7 g. (96%) ofblue-colored dye.

Example XI The procedure of Example II is followed using a 1% solutionof the 'dye of Example X. The fastness of the dyeing to soaping is onceagain much greater than that of the colorant from which the new dyestuffis prepared.

Example XII Example XIII The procedure of Example II is followed using a1% solution of the dye of Example XII. The fastness of the dyeing tosoaping is once again much greater than that of the colorant from whichthe new dyestuiI is made.

8 Example XIV The procedure of Example XII is repeated using 1,4- bis(3bromo 2 hydroxypropoxy) 4 anilinoanthraquinone as a starting material.There is obtained in good yield a violet dye.

Example XV The procedure of Example XII is repeated using a 2- bromo 1,4bis(3 bromo 2 hydroxyp-ropoxy)anthraquinone as a starting material.There is obtained in good yield a Weak yellow-orange dye.

Example X VI The procedure of Example XII is repeated using 1,4,5,8-tetrakis (3 brorno 2 hydroxypropoxy)anthraquinone as a startingmaterial. There is obtained in good yield a red-brown dye.

Example XVII The procedure of Example XII is repeated using 1,5- bis( 3brorno 2 hydroxypropoxy)anthraquinone as a starting material. There isobtained in good yield a Weak yellow-brown dye.

Example XVIII The procedure of Example XII is repeated using 1,4-bis- (3bromo 2 hydroxypropoxyethylamino) 5,8 bis- (3 bromo 2hydroxypropoxy)anthraquinone as a starting material. There is obtainedin good yield a blue dye.

Example XIX Copper tetra (4)-(p-hydroxyphenoxy)phthalocyanineiscondensed with epibromoliydrin according to the procedure in Example Ito form the tetrabrornohydrin in good yield. When the product so formedis reacted with an excess of N,N,N',N-tetramethylthiourea, an excellentyield of water-soluble blue dye is obtained.

Example XX The procedure of Example II is followed using a 1% solutionof the dye of Example XIX. The fastness of the dyeing to soaping is onceagain much greater than that of the colorant from which the dyestuif isprepared.

Example XXI 5-(2,4-dinitrophenylamino)-2-naphthol is reacted withepibromohydrin according to the procedure in Example I.

A mixture of 18.5 g. (0.040 mole) of the bromohydrin so formed, 47.2 g.(0.4-0 mole) of N,N,N-trirnethylthiourea, and 40 ml. of water is stirredat C. until a sample is water-soluble. After cooling and adding thereaction mixture to 500 m1. of acetone, the precipitated product istriturated well with acetone, washed with .fresh portions of the samesolvent and dried at 50 C. under vacuum. There'is obtained 17.8 g. (77%)of orange dye.

Example XXII The procedure of Example II is followed using a 1% solutionof the dye of Example XXI. The fastness of the dyeing to soaping is onceagain much greater than that of the colorant from which the dyestufi isprepared.

Example XXIII At 25 C., cotton yarn is immersed in a bath containing 2%(on the weight of the goods) of the dye prepared according to Example I.Sodium chloride on the weight of the goods) is added and the bath israised to 60 C. during one hour. During this time, a total of 24% (onthe weight of the goods) of trisodium phosphate is added gradually. Thedyed yarn is rinsed, soaped, and dried. It exhibits very good wetfastness.

Example XXIV Wool yarn is dyed for one hour at 88 C. in a 1:30 dyebathcontaining 10% of sodium carbonate (on the weight of the goods) and 2%of the dye prepared in Example 1. After rinsing, the dyed materialexhibits very good Wet fastness.

Alternatively, the yarn is immersed for one-half hour at 88 C. in a 2%solution of the dye prepared in Example I. There is then added 3% (onthe weight of the goods) of 85% formic acid and the dyeing is continuedfor another one-half hour. After rinsing, the goods are treated forone-half hour at 88 C. With a solution containing one gram of soap andfour grams of soda ash per liter. The goods are rinsed and dried. Thedyed yarn possesses very good Wet fastness.

Example XXV wherein Z is a water-insoluble dyestutf moiety selected fromthe group consisting of azo, anthraquinone, phthalocyanine and nitro; Rand R as individual substituents, are members selected from the groupconsisting of hydrogen and lower alkyl and, taken collectively,represent an alkylene bridge having from 2 to 3 carbon atoms, saidbridge connecting the N atoms to which R and R are attached; R and R aremembers selected from the group consisting of hydrogen and lower alltyl;and n is an integer having a value of from 1 to 4.

2. A dyestuft" of claim 1, wherein Z is azo, R R R and R are hydrogenand n is one.

3. A dyestutt" of claim 1, wherein Z is anthraquinone, R R R and R arehydrogen and n is two.

4. A dyestutf of claim 1, wherein Z is phthalocyanine, R R R and R arehydrogen and n is four.

5. A dyestuff of claim 1, wherein Z is nitro, R R R and R are hydrogenand n is one.

References Cited in the file of this patent UNITED STATES PATENTS2,645,641 Rent'rew et a1. July 14, 1953 2,664,427 Randall et al Dec. 29,1953 2,829,129 Semmens et a1. Apr. 1, 1958 TINTTTD STATES PATENT oTTIcE@EHHQATE 6F CEUMON Patent No 3,155,645 November 3, 196

David Taber et a1.

It is hereby certified that error appears in the above numbered patentrequiring correction and that the said Letters Patent should read ascorrected below.

Column 4, line 16, for "1-amino-2ethylmercapto-4hy" readl-amino-2-benzylmercapto-4hycolumn 6, line 51 for "dying" read drying(SEAL) Attest:

ERNEST W.

Attesting Ufficer EDWARD J. BRENNER Gommissioner of Patents UNITEDSTATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No, 3,155,645November 3, 1964 David Taber et a1.

ied that error appears in the above numbered pat- It is hereby certif nand that the said Letters Patent should read as ent requiring correctiocorrected below.

for "l-amino-2eethy1mercapto-4-hy-" Column 4, line 16,

column 6, line 51,

read l-amino-2 benzylmercapto4-hy for "dying" read drying Signed andsealed this 22nd day of February 1966.

(SEAL) Attest:

EDWARD J. BRENNER I Commissioner of Patents ERNEST W. SWIDER AttestingOfficer

1. A DYESTUFF OF THE FORMULA: